JPH0263054A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. contg. a free radical generator having high sensitivity for light having a specified wavelength, and to improve the sensitivity for such light of the photosensitive compsn. by incorporating a specified compd. into the compsn. CONSTITUTION:The title compsn. contains a jointed type compd. expressed by the formula: S-L-A as photo free radical generator. In the formula, S is a light absorbing moiety having 1,000 absorption coefft. or more for light having >=300nm wavelength; A is an active moiety generating a free radical by an interaction with a photoexcited S; L is a joining group for S to A. Suitable joining group L is an ester linkage, amide linkage, sulfonamide linkage, ether linkage, thioether linkage, amino linkage, or a combination of >=2 thereof. Thus, a photosensitive compsn. having high sensitivity for light ranging from near ultraviolet rays to visible rays, further to near infrared region, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition containing a novel compound that generates free radicals when exposed to light.

More specifically, a light-absorbing part and an active part that interacts with the light-absorbing part and generates free radicals when the light-absorbing part absorbs light and is excited are connected by a chemical bond. The present invention relates to a photosensitive composition containing a novel photo-free radical generator.

[Conventional technology]

Compounds that decompose to produce free radicals on exposure to light (
Free radical generators) are well known in the field of graphic arts. They are photoinitiators in photopolymerizable compositions,
It is widely used as a photoactive agent in free radical photographic compositions and as a photoinitiator for reactions catalyzed by photogenerated acids. Such free radical generators are used to make a variety of photosensitive materials useful in printing, duplication, copying and other imaging systems.

Conventional free radical generators include arylalkyl ketones such as penzoin atenopediethylacetophenone, oxime esters, acylphosphine oxides, diaryl ketones such as benzophenone, pendinobequinones, bisimidazoles, etc. has also been frequently used.

For information on these free radical generators, please refer to rJournal o
fRadiation Curing”, July 1987
Monthly issue, pages 6 to 16 and pages 18 to 31.

Furthermore, among the free radical generators, carbon tetrabromide, iodoporum, tribromoacetophenone, and the like are typical ones that generate halogen free radicals and have been widely used. S triazine compounds substituted with trichloromethyl groups have also been used, as described in US Pat. No. 4,619.998 and British Patent No. 1,388.492.

However, these free radical generators have the drawback of being decomposed only by light in a fairly limited wavelength range.

In other words, it was sensitive to the ultraviolet region, which is shorter than the dominant wavelength of commonly used light sources. Therefore, these compounds lack the ability to effectively utilize light in the near-ultraviolet to visible range emitted by a light source, and therefore have poor free radical-generating ability.

Furthermore, in recent years, in addition to the conventionally used ultraviolet light, the use of visible light or near-infrared lasers has been considered as a light source. In this case, the free radical generator needs to be sensitive to these various laser wavelengths.

In addition, in recent years, increased sensitivity to ultraviolet rays and methods of forming images using lasers have been studied, and UV projection exposure methods for printing plates, direct laser plate making, laser facsimile, holography, etc. have already reached the stage of practical use. Highly sensitive photosensitive materials are currently being developed to meet these needs. In order to develop these light-sensitive materials, it is essential to have a compound that can efficiently generate free radicals from the light source used, that is, light in the near-ultraviolet to visible and near-infrared regions.

Various attempts have been made to generate free radicals in response to light in the near-ultraviolet to visible range, and even in the near-infrared range. All of these attempts involved adding a combination of an activator capable of generating free radicals and some type of light absorber.

For example, in US Pat. No. 3,652,275, a chalcone or dibenzylacetone compound is used as a light absorbing agent, and a bisimidazole compound is used as an activator that generates free radicals. Further, in British Patent No. 2.020.297, a merocyanine dye is used as a light absorbing agent and a diphenyliodonium salt is used as an activator. Also, JP-A-58-403
Publication No. 02-c' it A thiopyrylium salt is used as a light absorbing agent, and a trichloromethyl-substituted S-) riazine compound is used as an activator, and JP-A-57-21401 uses a dialkylaminostilbene compound as a light absorbing agent.
Combinations of bisimidazole compounds are described as active agents. Also, JP-A-54-95687, JP-A-54-151024, and U.S. Patent No. 4.481.2.
In the specification of No. 76, merocyanine dye is used as a light absorbing agent, and trichloromethyl group-substituted 5 is used as an activator.
-) IJ azine compounds are used.

Also Polymer Engineering and
5science, Vol. 23, p. 122 (I983), ketocoumarin is used as a light absorber and N-phenylglycine is used as an activator.

Examples of other light absorbers and activators: F.

Written by εaton “＾dances in Photoc”
vol. 3, pp. 427-487 (I9
(1987), light absorbers include acridinium dyes such as acriflavine, xanthine dyes such as rose bengal, thionine, and thiazene dyes such as methylene blue, and activators include triethanolamine, hydrazine, and triphenyl. Amines such as amines, phosphorus compounds such as triphenylphosphine and tri-n-butylphosphine, sulfinic acids such as sodium P-)toluenesulfinate, sulfonic acid esters such as P-toluenesulfonic acid methyl ester, oxazole, imidazole heterocyclic compounds such as, erulate compounds such as dimedone,
Examples include tin compounds such as triptylbenzyltin, and others such as allylthiourea and N-phenylglycine.

Additional examples of light absorbers and activators are found in U.S. Pat. No. 4,743,529 and U.S. Pat.
3.530, in which anthracene, sulfocoumarin, and squalium dyes are used as light absorbers.
Pyridinium salts such as l-methoxy-4-phenylpyridinium tetrafluoroborate are also used as activators.

Systems in which light absorbers are added to these activators can generate free radicals in longer wavelength ranges than ever before, and photosensitive compositions containing these compounds are being considered for application in various fields. It's here. However, its ability to generate free radicals is still not sufficient, and there is currently a desire for photosensitive compositions that have even higher ability to generate free radicals.

[Problem to be solved by the invention]

Therefore, it is an object of the present invention to provide a photosensitive composition that contains a free radical generator that is highly sensitive to light having a wavelength of 300 nm or more and is highly sensitive to these lights.

Another object of the present invention is to provide a photopolymerizable composition containing a free radical generator that is highly sensitive to light rays of 3001 m or more.

[Means to solve the problem]

As a result of intensive research aimed at achieving the above object, the present inventors discovered that a certain photo-free radical generator efficiently generates free radicals against light rays of 300 nm or more, and the present invention was achieved. It is.

That is, the present invention is a photosensitive composition characterized by containing a linked compound represented by general formula (I).

5-L-A(I) In the general formula (I), S is a light-absorbing moiety that has an absorption coefficient of 1000 or more at wavelengths longer than 300 nm, and A has an activity that interacts with photoexcited S to generate free radicals. and L is a linking group that connects S and A. Preferred linking groups represented by are ester bonds, amide bonds, sulfonamide bonds, ether bonds, thioether bonds, amino bonds, or a combination of two or more of these.

Examples of compounds containing a light absorbing portion S having an absorption coefficient of 1000 or more at long wavelengths of 300 nm or more include light absorbers that have conventionally been used in combination with an activator. For example, the aforementioned chalcone or dibenzylacetone compounds,
In addition to merocyanine dyes, thiopyrylium or pyrylium dyes, dialkylaminostilbene compounds, acridinium dyes, xanthine dyes, thiazene dyes, cyanine dyes, squalium dyes and thioxanthone can be mentioned.

Other examples include polynuclear aromatic compounds such as anthracene, phenanthrene, pyrene, acridine, carbazole,
Mention may be made of polynuclear heteroaromatic compounds such as phenothiazines and their derivatives.

Compounds with active moieties that interact with photoexcited S to generate free radicals include the above-mentioned bisimidazole compounds, onium compounds such as diphenyliodonium and triphenylsulfonium salts, and trichloromethyl-substituted-3-)riazine. Compounds, N-phenylglycine, amines such as triethanolamine and hydrazine, phosphorus compounds such as triphenylphosphine and tri-n-butylphosphine, sulfinic acids such as sodium P-toluenesulfinate, and methyl P-toluenesulfonate. sulfonic acid esters such as, heterocyclic compounds such as oxazole and imidazole, erulate compounds such as dimedone, tin compounds such as tributylbenzyltin, pyridinium salts such as 1-methoxy-4-carbomethoxypyridinium tetrafluoroborate (about this is “Re5e”
archDisclosure”Vo1.200.1
(Listed in December 980 Item 20036)
, allylthiourea, oxime ester, triphenyl-n-butylborate, and other borane compounds, and the residues of these compounds can be used as the active moiety A of the novel free radical generator according to the present invention. It can be used as

Preferred examples of the bonds connecting the light absorbing part S and the active part A include ester bonds represented by the following formulas (a) and (5) C-0-(a) 0-C-0 (b); Formula (C), (d), (e), (f) -N- R (C) C-N-3o□ - R (e) (In the formula, R represents hydrogen, alkyl, or aryl.

), sulfonamide bonds represented by the following formula (g) SO□ -N-(in which R represents hydrogen, alkyl or aryl), ether bonds,
Examples include thioether bond and amino bond.

Among the compounds represented by the general formula (I), particularly preferred are compounds in which the light absorption part S is a merocyanine dye, a cyanine dye,
Squarium dye, acridinium dye, polynuclear aromatic compound, and polynuclear heteroaromatic compound residue, active part A is S-triazine or l-alkoxypyridinium residue containing trichloromethyl group, and linking group is ester The compound is one of a bond, an amide bond, and a sulfonamide bond.

The merocyanine dye used in the synthesis of the compound represented by the general formula (I) is a generally known merocyanine dye containing a functional group necessary for linking the active moiety A. Generally known merocyanine dyes include those described by FlM Hamer et al.
[1YIES AN[] RBLATEII
CQMPOIJNIIIS 41964, pages 511-6
This is the compound described on page 11. An example of such a merocyanine dye is shown by the following general formula (n). However, the present invention is not limited to those represented by these general formulas (n).

In the formula, R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an allyl group, or a substituted allyl group, and Y is 10-
1-3- -NR'- (here, R plate has the same meaning as R1 above), -3e -C(CL)*- and -C)l=c
A divalent atom or atomic group selected from H-. Furthermore, both R1 and R2 may form a ring together with the carbon atom to which they are bonded.

n represents 0.1 or 2.

Gl and G2 may be the same or different, and each represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group,
It represents a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a fluoroalkylsulfonyl group. However, Gl and 62 do not become hydrogen atoms at the same time. Further, G1 and G2 may form a ring consisting of a nonmetallic atom together with the carbon atom to which they are bonded.

When G1 and 62 form a ring consisting of a nonmetallic atom together with the carbon atom to which they are bonded, the ring is one that is usually used as an acidic nucleus in merocyanine dyes, and examples include the following.

(a) 1,3-dicarbonyl nucleus, such as 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione (b) Pyrazolinone nucleus, e.g. 3-methyl-1-phenyl-2-pyrazoline-5-
one, 1-phenyl-2-pyrazolin-5-one, 1-
(2-Benzothiazolyl)-3-methyl-2-pyrazolin-5-one (C) Isoxacillinone nucleus, e.g. 3-phenyl-2-yneoxazolin-5-one, 3-methyl-2-
Inoxazolin-5-one etc. (d) Oxindole nucleus, e.g. 1-alkyl-2,3-dihydro-2-
Oxindole (e) 2,4.6-)liketohexahydrobyrimidine nucleus, e.g. barbituric acid or 2-
Thiobarbic acid and its derivatives. Such derivatives include 1-alkyl derivatives such as 1-methinope l-ethyl;
, 3-diethinobe 1,3-dibutyl, etc., 1,3-dialkyl derivatives, 1. 3-diphenyl, 1.3-di(p-chlorophenyl), 1. 1゜3-diaryl derivatives such as 3-di(p-ethoxycarbonylphenyl), 1-ethyl-
Examples include 1-alkyl-3-aryl bodies such as 3-phenyl.

(f) 2-thio-2,4-thiazolidinedione nuclei, such as rhodanine and its derivatives. Such derivatives include 3
Examples include 3-alkylrhodanines such as -ethylrhodanine and 3-alkylrhodanine, and 3-arylrhodanines such as 3-phenylrhodanine.

((to) 2-thio-2,4-oxazolidinedione (
2-thio-2,4-(3H,5H)-oxazoledione) nucleus, e.g. 2-ethyl-2-thio-2,4-oxazolidinedione Co., Ltd. Thianaphthynone nucleus, e.g. 3(2H)-thianaphthynone and 3( 2H)-thianaphthynone-1,1-
Dioxide (I) 2-thio-2,5-thiazolidinedione nucleus, e.g. 3-ethyl-2-thio-2,5-thiazolidinedione (i) 2,4-thiazolidinedione nucleus, e.g. 2°4-
Thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4thiazolidinedione (t)thiazolidinone nucleus, e.g. 4-thiazolidinone,
3-ethyl-4-thiazolidinone (I) 4-thiazolinone nucleus, such as 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one (e) 2-imino-2 -Oxozolin-4-one (hydantoin) nucleus (n) 2,4-imidazolidinedione (hydantoin)
Nuclei, e.g. 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione (0) 2-thio-2,4-imidazolidinedione (2-
thiohydantoin) nucleus, e.g. 2-thio2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione (p) 2-imidacylin-5-one nucleus, e.g. 2-n- Propyl-mercapto-2-imidacillin-5-one (q) Furan-5-one However, a merocyanine dye represented by general formula (II) is used as the light-absorbing moiety of the novel photofree radical generator used in the present invention. For R1, R2, R3, G1, G2
Any of these is a functional group necessary to react with a compound containing an active part to form a bond connecting the light-absorbing part and the active part, such as a carboxyl group, a hydroxyl group, an amino group, a sulfonyl group, or an incyanate group. It is necessary to have at least one of a group, a thioisocyanate group, a thiol group, etc.

S-) containing a trichloromethyl group, which can be the active moiety A of the compound of general formula (I)! The J azine compound is represented by the following general formula (II[).

"In the formula, R4 and R5 represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. However, either R4 or R5 represents the light-absorbing moiety S.
contains at least one functional group necessary to form a linking group by reacting with a compound containing .

Substituted alkyl groups represented by R4 and R5 include trichloromethyl and trifluoromethyl, substituted aryl groups include 4-styrylphenyl and 4-(substituted)styrylphenyl, and substituted alkenyl groups include styryl and substituted styrinopearyl. Examples of the group include polycyclic aromatic compound residues such as naphthyl, and heteroaromatic compound residues such as thiofuran. Furthermore, examples of the functional group necessary for linking with the light absorbing part S include those similar to those used in general formula (II).

Some examples of the novel photo-free radical generator used in the present invention are described below (Ph represents a phenyl group).

However, it goes without saying that the present invention is not limited to the following compounds.

L The free radical generator represented by general formula (I) is particularly useful when used as a photoinitiator in a photopolymerizable composition.

When the free radical generator represented by general formula (I) is used in a photopolymerizable composition, the photopolymerizable composition contains a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and the necessary components. If so, it is composed of a linear organic high-molecular polymer, and is particularly useful for photosensitive layers of photosensitive printing plates, photoresists, etc.

The amount of the free radical generator in the photopolymerizable composition of the present invention is 0.01 based on the total of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer added as necessary.
It is preferably used in a range of 60% by weight. More preferably, good results are obtained with 1% to 30% by weight.

The polymerizable compound having an ethylenically unsaturated bond used in the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure. For example, it has chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like.

Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol as acrylic esters. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,
Examples include tri(acryloyloxyethyl)isocyanurate and polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipene querrythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-[p-(3-methacrylate) Oxy-
Examples include 2-hydroxypropoxy)phenylfudimethylmethane, bis-1''p-(acryloxyethoxy)phenylfudimethylmethane, and the like.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1.
Examples include 6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

The amount of these used is 5% by weight or more, preferably 10% to 99.5% by weight based on the total components.

As the linear organic polymer that can be used in the present invention, any linear organic polymer can be used as long as it is naturally compatible with the photopolymerizable ethylenically unsaturated compound. I don't mind if you do.

Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water should be selected so that it can be developed in water or weakly alkaline water.

For example, water development becomes possible when a water-soluble organic high molecular weight polymer is used. As such linear organic polymers,
Addition polymers having carboxylic acid in the side chain, such as JP-A-5
9-44615, JP 54-34327, JP 58-12577, JP 54-25957, JP 54-92723 1, JP 59-53836,
Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, which are described in JP-A No. 59-71048,
Examples include partially esterified maleic acid copolymers. Similarly, there are acidic cellulose derivatives having carboxylic acid in their side chains. In addition to these, addition polymers having hydroxyl groups to which a cyclic acid anhydride is added are useful. In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as necessary] copolymers and [allyl (meth)acrylate/(meth)acrylic acid/as necessary and other addition-polymerizable vinyl monomers] copolymers are preferred.

Any amount of these linear organic high molecular weight polymers can be mixed into the entire composition. However, if it exceeds 90% by weight, favorable results will not be obtained in terms of the strength of the formed image.

Further, if necessary, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added and floated on the surface of the photosensitive layer in order to prevent polymerization inhibition by oxygen. The amount of higher fatty acid derivative added is about 0.5% to about 10% by weight of the total composition.
Weight percent is preferred. Furthermore, dyes or pigments may be added for the purpose of coloring the photosensitive layer. The amount of dyes and pigments added is preferably about 0.5% to about 5% by weight of the total composition.

In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

When the above photopolymerizable composition is applied and used, a dimensionally stable plate-like material is used as the support. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), and materials such as aluminum (including aluminum alloys), zinc, copper, etc. sheets of metal, and also films of plastics, such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include paper or plastic film laminated or vapor-deposited with the metals mentioned above.

Among these supports, aluminum plates are particularly preferred for producing photosensitive lithographic printing plates because they are extremely dimensionally stable and inexpensive. In addition, the special public official 1832-1832
Also preferred is a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 7.

In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably.

On the layer of the photopolymerizable composition provided on the support, an oxygen-blocking material such as polyvinyl alcohol, acidic cellulose, etc. is used to prevent the polymerization inhibiting effect caused by oxygen in the air. A protective layer of a superior polymer may also be provided. A method for applying such a protective layer is described, for example, in U.S. Pat.
It is described in detail in Publication No. 29.

An image can be obtained by imagewise exposing a photosensitive material using the photopolymerizable composition of the present invention and removing unexposed areas of the photosensitive layer with a developer. Preferred developing solutions when using these photopolymerizable compositions to create lithographic printing plates include:
Examples include the developer described in Japanese Patent Publication No. 57-7427, which contains sodium silicate, potassium silicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Inorganic alkaline agents such as trisodium phosphate, sodium diphosphate, ammonium triphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, sodium carbonate, aqueous ammonia, monoethanol or jetanolamine, etc. An aqueous solution of an organic alkaline agent such as is suitable. The concentration of the alkaline solution is 0.1
It is added in an amount of up to 10% by weight, preferably 0.5 to 5% by weight.

In addition, the alkaline aqueous solution may contain surfactants, benzyl alcohol, 2-phenoxyethanol, 2
- Small amounts of organic solvents such as butoxetanol may be included. For example, those described in US Pat. No. 3,375,171 and US Pat. No. 3,615,480 can be mentioned.

〔Effect of the invention〕

The photosensitive composition using the novel photo-free radical generator of the present invention has high sensitivity to actinic light in a wide range from near-ultraviolet light to visible and near-infrared light.

Therefore, light sources include ultra-high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, cannon lamps, metal halide lamps, various visible, ultraviolet, and near-infrared laser lamps, fluorescent lamps, tungsten lamps, and sunlight. can be used.

〔Example〕

The present invention will be explained below with reference to Examples and Synthesis Examples, but the present invention is not limited thereto.

<Synthesis example> Synthesis of compound (I) Compound (I) is a compound (I) having a light absorption moiety represented by the following formula.
-3) and a compound (IA) having an active moiety.

The synthesis method is described below.

3.9 g of (IA) and thionyl chloride 6- were mixed and heated under reflux for 30 minutes. Next, excess thionyl chloride was distilled off under reduced pressure, and then 2.8 g of (I-3) and 500 rnl of anhydrous tetrahydrofuran were added, heated under reflux for 30 minutes, and then the solution was cooled on ice.

2.2 g of N,N-dimethylaminopyridine was added to this solution and stirred at room temperature for 1 hour. 2I! The reaction solution was added with 1 ml of concentrated hydrochloric acid! of water, and the resulting solid was collected by filtration.

The solid was recrystallized using ethyl acetate to obtain 145 g of crystals.

Melting point 229-230℃ UV spectrum (in acetonitrile) 429nm (ε: 6.29X10') 281nm (ε: 3.55X10') Elemental analysis Calculated value as C27H19N5S303C1s (%')
C: 42.10 H: 2.49 N: 9.09
Cj! :27.61 Measured value (%) C:41.98
H: 2.40 N: 9.13 CA: 27.40
<Example> A photosensitive solution having the following composition was applied onto a 100 μm polyethylene terephthalate film using a spinner and dried at 100° C. for 2 minutes to form a photosensitive layer. Note that the rotation speed of the spinner was 100 revolutions/minute.

・Pentaerythritol tetraacrylate 1.4g
- Benzyl methacrylate and methacrylic acid copolymer (copolymerization molar ratio 73:2T> 1.3 g - Photo free radical generator 0.13 mmIJ mole - Methyl ethyl ketone 12 g - Propylene glycol monomethyl ether acetate 12 g On this photosensitive layer Polyvinyl alcohol (saponification degree 86.5-8
A 3 wt % aqueous solution of 9 mol %, polymerization degree 1000) was applied and dried at 100° C. for 2 minutes.

The photosensitivity test was conducted as follows.

The light source is a 500W xenon lamp and an interference filter (431.5±15nm, T4) that passes 430nm light.
5.5% (manufactured by Kenko).

For sensitivity measurement, Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd., transmission optical density of the first stage is 0.05 and sequentially 0.
．． (Step tablet that increases by 15 and has up to 15 steps)
It was done using .

The amount of light passing through the first stage of this step guide was 33.92 mj/cut when exposed for 1000 seconds.

Development was performed by immersing the film in the following developer at 25° C. for 1 minute.

Sensitivity evaluation is obtained by reading the maximum number of steps in the remaining step image after photocuring. More precisely, the UV absorption spectrum of each stage of the obtained step image is measured, the density (OD) value at the maximum absorption of the obtained absorption is determined, and this density value (OD) is calculated based on the amount of irradiated light. By plotting, the sensitivity E (Dlo) when the unexposed OD decreases to 10% and the sensitivity E (D90) when it decreases to 90% can be determined.

The results are shown in Table 1.

Table 1 Comparative Examples> As a comparison of Example 1, the following compounds (I-3') and (IA') were used instead of the photofree radical generator compound (I).
0.13 μIJ mole of each was added as a photofree radical generator.

In addition, as a comparison of Example 2, a photofree radical generator compound (5)
Instead, the following compounds (5-3') and (I-AM
0. l 3 mi! J mol was added as a photo-free radical generator.

nLsill) The results are shown in Table 2.

A photosensitive layer was prepared in the same manner as in Table Example 1.2, and the sensitivity of the photosensitive layer was evaluated. The photosensitive layer was exposed using an interference filter (490nm±12r1m) that passes light at 4900m.

The exposure time was 1000 seconds. The exposure amount at this time is 3
It was 6.2 μW/cffl.

As a comparative example, the following compounds were each used as a photo-free radical generator at a concentration of 0.13 mi! A photosensitive layer prepared by adding J mol was used.

From Tables 1 and 2, it can be seen that Examples 1 and 2 using the photo-free radical generator of the present invention containing a light-absorbing part and an active part in one molecule have a compound having a light-absorbing part and an active part. It can be seen that the sensitivity is much higher than that of Comparative Examples 1 and 2 in which the compound was used in combination.

Example 3 Table 3 shows the results obtained except that compound αυ was used as a photo-free radical generator.

Table 3 Example 4 A photosensitive layer was prepared in the same manner as in Example 1.2, except that Compound α was used as a photo-free radical generator, and the sensitivity of the photosensitive layer was evaluated. The photosensitive layer was exposed using an interference filter that passes 350 nm light.

The exposure time was 1000 seconds.

As a comparative example, the following compounds were used as photo-free radical generators and bioagents at 0.13 mi! A photosensitive layer prepared by adding j moles of the compound was used.

table The results obtained are shown in Table 4.

Claims (1)

[Scope of Claims] 1. A photosensitive composition containing a compound represented by general formula (I) as a photo-free radical generator. S-L-A (I) In the formula, S is a light-absorbing part that has an absorption coefficient of 1000 or more at wavelengths longer than 300 nm, and A is an active part that interacts with photoexcited S to generate free radicals. , L is S and A
It is a linking group that connects. 2. Photopolymerization characterized by comprising a photo-free radical generator represented by the general formula (I) according to claim 1 and a monomer having at least one ethylenically unsaturated group capable of radical polymerization. sexual composition.